CA1082162A - Crystalline type-a zeolite powder iii - Google Patents
Crystalline type-a zeolite powder iiiInfo
- Publication number
- CA1082162A CA1082162A CA289,971A CA289971A CA1082162A CA 1082162 A CA1082162 A CA 1082162A CA 289971 A CA289971 A CA 289971A CA 1082162 A CA1082162 A CA 1082162A
- Authority
- CA
- Canada
- Prior art keywords
- na2o
- al2o3
- weight
- sio2
- per litre
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000843 powder Substances 0.000 title claims abstract description 15
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 title claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000001228 spectrum Methods 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 7
- 238000000034 method Methods 0.000 claims description 19
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 15
- 238000005496 tempering Methods 0.000 claims description 12
- 238000010008 shearing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- -1 alkali metal aluminate Chemical class 0.000 claims 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims 1
- 239000003599 detergent Substances 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 239000010452 phosphate Substances 0.000 abstract description 4
- 239000002808 molecular sieve Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004435 Oxo alcohol Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 4
- VXJCGWRIPCFWIB-UHFFFAOYSA-N hexadecasodium tetrasilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] VXJCGWRIPCFWIB-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229940115440 aluminum sodium silicate Drugs 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000429 sodium aluminium silicate Substances 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/24—LTA, e.g. A, alpha, ZK-4, ZK-21, ZK-22
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a crystalline type-A
zeolite powder having the composition 1.0 ? 0.2 M2/nO : Al2O3 :
1.85 ? 0.5 SiO2 ? y H2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50% by weight of particles of a size below a maximum of 4.3 µm as well as having the following particle spectrum
The present invention provides a crystalline type-A
zeolite powder having the composition 1.0 ? 0.2 M2/nO : Al2O3 :
1.85 ? 0.5 SiO2 ? y H2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50% by weight of particles of a size below a maximum of 4.3 µm as well as having the following particle spectrum
Description
The [~rcsent inv~ntion relatcs to a crystalline type-l~ zeolite powder having the composition 1.0 + 0.2 M2/nO : A12O3 : 1.85 +
0.5 SiO2 y ll2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50~ by weight of particles of a size below a maximum of 4.3 ~m. The present invention a]so relates to the process for producing the crystalline zeolite powder by means of hydrothermal crystallization of an alkali-aluminate-silicate mixture and to the use of this 2eolite powder in washing, rinsing and cleansing agents.
Zeolitic molecular sieves with their specific properties for ion exchange and adsorption have been known for a long time.
Their synthesis is based on heating an aqueous synthesis mixture having the components a Na2O x b A12O3 x c SiO2 to temperatures between 50 and 300C. Depending on the composition of the starting -mixture, reaction temperature and reaction time differently structured compounds having the general formula Nax Alx Siy 2 (x+y) n H2O are obtained. These compounds can be distinguished by _-their X-ray spectra. Sodium can be replaced by other monovalent or divalent rnetal cations.
For use as adsorbents, catalyst supports or ion exchangers the molecular sieves are converted into molded articles by means of a suitable binder. The production of the molded articles means a great technical expenditure while simultaneously reducing the effect as a result of the proportion of binder. The rate of reaction also is substantially slowed down due to the long diffusion paths, whereby, for example, the drying of organic liquids is rendered cumbersome. Therefore, for many uses it makes sense to apply the molecular sieve in the form of a powder.
The fact that in the molecular-sieve synthesis crystals having an average diameter above approximately 2 ~m are obtained - while a substantial proportion, usually from 3 to 12~ by weight, ~ .
08216;Z
have a maximum particle size above 45 llm is common to the known methods of production (for example, German Patent 1 038 017).
This proportion is known as grit, which, according to DIN 53 580, is determined by wet screening according to Mocker. In a product typical of this process it is found that approximately 25% by weight of particles have diameters below 10 ~m and 50% by weight have particle diameters of 13 ~m (D.W. Breck, Zeolite Molecular Sieves, page 388, John Wiley + Sons, New York, London, Sidney, Toronto, 1974).
The present invention provides a process by means of which powdered, zeolitic type-A molecular sieves for use as --ion exchangers, for example, as water softeners, can be synth-esized without a proportion of grit (particles < 45 ~m) and with smaller particle sizes. The absence of grit as well as a smaller particle size is indispensable for the use of these molecular -sieves within the scope of the invention, for example, as a phosphate substitute in washing, rinsing and cleansing agents.
Washing and cleansing procedures, particularly in machines, require that the molecular sieve remains in suspension in the wash liquor (due to low tendency for sedimentation) in order to attain rinsing without residues on completion of the procedure.
According to the present invention there is provided a crystalline type-A zeolite powder having the composition 1.0 +
0.2 M2/n :A12O3 : 1.85 + 0.5 SiO2 y H2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50% by weight of particles below a maximum of 4.3 ~m - as well as having the following particle spectrum fraction proportion (~m) (% by weight) < 3 18 to 38 < 5 70 to 82 <10 93 to 99 <15 96 to 100 -.
10~321t~2 The pr~sent invention aL.so provides a proc~ss for produciny the crystalline zoelite powder by hydrothermal crystallization of an al]cali metal aluminate/
water/silicate synthesis mixture containing sio2, A1203, Na20 and water, if required with a subsequent tempering stage~ During the crystallization or in the tempering stage stirring may be replaced by the action of shearing force~. This process is characterized in that an al~ali metal silicate solution is added within 10 to 200 minutes while stirring to an aqueous sodium aluminate liquor having a temperature of 30 to 100C and containing 100 g of A1203 per litre and 1 to 200 g of Na20 per litre so that a r.
clear reaction mixture having the composition SiO2/A1203 = 50 to 10000, Na20/SiO2 = 0.2 to 20 and ~l20/Na20 = 4 to 300 is obtained, whereupon,over a period of 5 to 200 minutes, a sodium aluminate liquor having a temperature of 30 to 100C and containing 10 to 250 g of Na20 per litre and 10 to 200 g of A1203 per litre is added while stirring and that the synthesis mixture thus obtained is crystallized at a temperature between 20 and 175C within at least 15 minutes.
In the process according to the invention, stirring may be replaced by the action of shearing forces. Convcntional devices can be used for this purpose. This conventional measure increases the particle fineness but is not required for carrying out the process according to the invention.
In a preferred manner of carrying out the process according to the invention the sodium-aluminate liquor having a content of 10 to 250 g of Na20 per litre and 10 to 200 g of A1203 per litre may be added to the reaction mixture in stages, for example in two stages, the rate of addition in the second stage beiny 2 to 10 times higher than that in the first stage.
In the process according to the invention shearing forces may be allowed to act on the synthesis mixture, which can contain - ~0821~i2 the individual components in molar ratios as they are used in known processes (for example, German Patent 1 038 017 and laid-open German Specification 1 095 795), during the crystallization and possibly during the subsequent tempering stage.
By "shearing" is meant any comminuting mechanical stress of discrete particles in suspension, i.e., a stress which is due primarily to real shearing action. The shearing can be carried out continuously or discontinuously. A turbine impeller, for example, the EKATO (a trade mark) turbine impeller, is preferred as the shear device. However, shearing can also be performed with a toothed-disc dissolver, dispensing pump, rotary pump, etc. ~`, While inthe present case, the crystallization can be carried out, for example, at 9~C it has been found to be advantageous to carry out the tempering at a temperature between 85 and 105C in the crystallization mother liquor. Tempering times between 0.2 and 6,preferably between 0.8 and 4, particularly 3 hours are favourable. The tempering time commences at the point at which the crystallization is completed. This point is evident from the development of maximum ion exchange capacity, on attaining maximum X-ray line intensity and an adsorption of water vapour of approximately 22.5%. In practice the tempering time is based on an empirical value determined by means of optimum formulation.
Shearing forces acting to the end of the crystallization phase can be so intensified that the average particle diameter can be reduced to very small values. The values for the maximum particle size and its percentage in the product can also be - reduced. However, shearing carried out during the tempering stage exclusively influences the maximum particle size and its proportion inthe product.
Finally the invention relates to the use of the crystalline type-A zeolite powder according to the invention as --- 101~2162 an ion exchanger, for example, for the softening of water, particularly as a phosphate substitute in washing, rinsing and cleansing agents.
These detergents are combinations of surface-active crude washing substances. However, in most cases they also contain other substantially inorganic additives, which contribute to a successful washing procedure and are necessary for the ~-productionprocessand for the external quality of the production.
Depending on the use concerned the composition of the detergents varies and depends particularly on the fiber type, coloration and washing temperature. It also depends on whether the washing operation is carried out by hand, for example, in a tub, in a '~
household washing machine or in a laundry. Most detergents are pourable powders. Ilowever, liquid and pasty products are also available (see Ullmann's Enzyklopadie der technischen Chemie, Third Edition, Vol. 18 Urban + Schwarzenberg, Munich 1967).
The crystalline type-A zeolite powder according to the invention has the advantage that it is free from grit and contains smaller particles even during its production. Therefore, when using it as a phosphate substitute in washing and cleansing agents it can be easily kept in suspension in the liquors concerned and can be rinsed out with particular ease from washing and cleaning machines and their charge without leaving residues.
The present invention will be further described by way of the following Examples.
Example 1 . .
300 litres of sodium tetrasilicate (~ = 1.35 kg per litre) containing 7.4~ of Na2O and 25.7~ of SiO2 are added within 40 minutes to 550 litres of a sodium aluminate liquor in a tub of -~
0.5 SiO2 y ll2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50~ by weight of particles of a size below a maximum of 4.3 ~m. The present invention a]so relates to the process for producing the crystalline zeolite powder by means of hydrothermal crystallization of an alkali-aluminate-silicate mixture and to the use of this 2eolite powder in washing, rinsing and cleansing agents.
Zeolitic molecular sieves with their specific properties for ion exchange and adsorption have been known for a long time.
Their synthesis is based on heating an aqueous synthesis mixture having the components a Na2O x b A12O3 x c SiO2 to temperatures between 50 and 300C. Depending on the composition of the starting -mixture, reaction temperature and reaction time differently structured compounds having the general formula Nax Alx Siy 2 (x+y) n H2O are obtained. These compounds can be distinguished by _-their X-ray spectra. Sodium can be replaced by other monovalent or divalent rnetal cations.
For use as adsorbents, catalyst supports or ion exchangers the molecular sieves are converted into molded articles by means of a suitable binder. The production of the molded articles means a great technical expenditure while simultaneously reducing the effect as a result of the proportion of binder. The rate of reaction also is substantially slowed down due to the long diffusion paths, whereby, for example, the drying of organic liquids is rendered cumbersome. Therefore, for many uses it makes sense to apply the molecular sieve in the form of a powder.
The fact that in the molecular-sieve synthesis crystals having an average diameter above approximately 2 ~m are obtained - while a substantial proportion, usually from 3 to 12~ by weight, ~ .
08216;Z
have a maximum particle size above 45 llm is common to the known methods of production (for example, German Patent 1 038 017).
This proportion is known as grit, which, according to DIN 53 580, is determined by wet screening according to Mocker. In a product typical of this process it is found that approximately 25% by weight of particles have diameters below 10 ~m and 50% by weight have particle diameters of 13 ~m (D.W. Breck, Zeolite Molecular Sieves, page 388, John Wiley + Sons, New York, London, Sidney, Toronto, 1974).
The present invention provides a process by means of which powdered, zeolitic type-A molecular sieves for use as --ion exchangers, for example, as water softeners, can be synth-esized without a proportion of grit (particles < 45 ~m) and with smaller particle sizes. The absence of grit as well as a smaller particle size is indispensable for the use of these molecular -sieves within the scope of the invention, for example, as a phosphate substitute in washing, rinsing and cleansing agents.
Washing and cleansing procedures, particularly in machines, require that the molecular sieve remains in suspension in the wash liquor (due to low tendency for sedimentation) in order to attain rinsing without residues on completion of the procedure.
According to the present invention there is provided a crystalline type-A zeolite powder having the composition 1.0 +
0.2 M2/n :A12O3 : 1.85 + 0.5 SiO2 y H2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50% by weight of particles below a maximum of 4.3 ~m - as well as having the following particle spectrum fraction proportion (~m) (% by weight) < 3 18 to 38 < 5 70 to 82 <10 93 to 99 <15 96 to 100 -.
10~321t~2 The pr~sent invention aL.so provides a proc~ss for produciny the crystalline zoelite powder by hydrothermal crystallization of an al]cali metal aluminate/
water/silicate synthesis mixture containing sio2, A1203, Na20 and water, if required with a subsequent tempering stage~ During the crystallization or in the tempering stage stirring may be replaced by the action of shearing force~. This process is characterized in that an al~ali metal silicate solution is added within 10 to 200 minutes while stirring to an aqueous sodium aluminate liquor having a temperature of 30 to 100C and containing 100 g of A1203 per litre and 1 to 200 g of Na20 per litre so that a r.
clear reaction mixture having the composition SiO2/A1203 = 50 to 10000, Na20/SiO2 = 0.2 to 20 and ~l20/Na20 = 4 to 300 is obtained, whereupon,over a period of 5 to 200 minutes, a sodium aluminate liquor having a temperature of 30 to 100C and containing 10 to 250 g of Na20 per litre and 10 to 200 g of A1203 per litre is added while stirring and that the synthesis mixture thus obtained is crystallized at a temperature between 20 and 175C within at least 15 minutes.
In the process according to the invention, stirring may be replaced by the action of shearing forces. Convcntional devices can be used for this purpose. This conventional measure increases the particle fineness but is not required for carrying out the process according to the invention.
In a preferred manner of carrying out the process according to the invention the sodium-aluminate liquor having a content of 10 to 250 g of Na20 per litre and 10 to 200 g of A1203 per litre may be added to the reaction mixture in stages, for example in two stages, the rate of addition in the second stage beiny 2 to 10 times higher than that in the first stage.
In the process according to the invention shearing forces may be allowed to act on the synthesis mixture, which can contain - ~0821~i2 the individual components in molar ratios as they are used in known processes (for example, German Patent 1 038 017 and laid-open German Specification 1 095 795), during the crystallization and possibly during the subsequent tempering stage.
By "shearing" is meant any comminuting mechanical stress of discrete particles in suspension, i.e., a stress which is due primarily to real shearing action. The shearing can be carried out continuously or discontinuously. A turbine impeller, for example, the EKATO (a trade mark) turbine impeller, is preferred as the shear device. However, shearing can also be performed with a toothed-disc dissolver, dispensing pump, rotary pump, etc. ~`, While inthe present case, the crystallization can be carried out, for example, at 9~C it has been found to be advantageous to carry out the tempering at a temperature between 85 and 105C in the crystallization mother liquor. Tempering times between 0.2 and 6,preferably between 0.8 and 4, particularly 3 hours are favourable. The tempering time commences at the point at which the crystallization is completed. This point is evident from the development of maximum ion exchange capacity, on attaining maximum X-ray line intensity and an adsorption of water vapour of approximately 22.5%. In practice the tempering time is based on an empirical value determined by means of optimum formulation.
Shearing forces acting to the end of the crystallization phase can be so intensified that the average particle diameter can be reduced to very small values. The values for the maximum particle size and its percentage in the product can also be - reduced. However, shearing carried out during the tempering stage exclusively influences the maximum particle size and its proportion inthe product.
Finally the invention relates to the use of the crystalline type-A zeolite powder according to the invention as --- 101~2162 an ion exchanger, for example, for the softening of water, particularly as a phosphate substitute in washing, rinsing and cleansing agents.
These detergents are combinations of surface-active crude washing substances. However, in most cases they also contain other substantially inorganic additives, which contribute to a successful washing procedure and are necessary for the ~-productionprocessand for the external quality of the production.
Depending on the use concerned the composition of the detergents varies and depends particularly on the fiber type, coloration and washing temperature. It also depends on whether the washing operation is carried out by hand, for example, in a tub, in a '~
household washing machine or in a laundry. Most detergents are pourable powders. Ilowever, liquid and pasty products are also available (see Ullmann's Enzyklopadie der technischen Chemie, Third Edition, Vol. 18 Urban + Schwarzenberg, Munich 1967).
The crystalline type-A zeolite powder according to the invention has the advantage that it is free from grit and contains smaller particles even during its production. Therefore, when using it as a phosphate substitute in washing and cleansing agents it can be easily kept in suspension in the liquors concerned and can be rinsed out with particular ease from washing and cleaning machines and their charge without leaving residues.
The present invention will be further described by way of the following Examples.
Example 1 . .
300 litres of sodium tetrasilicate (~ = 1.35 kg per litre) containing 7.4~ of Na2O and 25.7~ of SiO2 are added within 40 minutes to 550 litres of a sodium aluminate liquor in a tub of -~
2 cu m capacity. Said liquor has a temperature of 70C and contains 7.4% of Na2O and 25.7~ of SiO2. The solution then is clear. t 100 litres of an aqueous sodium-aluminate liquor having a temperature of 70C and containing 160 g of Na2O per 10E~2162 , . .
litre and 106 g of A12O3 per litre are added first to the solution in 15 minutes, whereupon 900 litres of the same liquor are added in 60 minutes. The reaction mixture is heated to 85C and is crystallized for 3 hours. ~ pure type-~ zeolite having the following particle spectrum is obtained:
fraction proportion (% by weight) < 3 ~m 21%
< 5 ~m 76%
<10 llm 97%
<15 llm 98%
The proportion of 50% by weight is below 3.8 ~m. ~, The particle size is determined by measuring with the Coulter counter.
- Examp e 2 Perborate-Containing Detergent 45.0% by weight of sodium aluminium silicate obtained according to example 1 (dried for 6 hours at 90C, water content 16.8% by weight), 20.0% by weight of sodium perborate, 35.0% of a detergent powder, produced,for example, by -hot-air drying and having the following composition:
21.0% by weight of ABS (dodecyl benzene sulphonate), 7.5% by weight of ethoxylated tallow alcohol (1 mole of tallow alcohol + 14 moles of ethylene oxide), 7.2% by weight of soap (sodium salt of saturated substantiallY C18-C22 fatty acids), 9% by weight of sodium tetrasilicate (Na2O
litre and 106 g of A12O3 per litre are added first to the solution in 15 minutes, whereupon 900 litres of the same liquor are added in 60 minutes. The reaction mixture is heated to 85C and is crystallized for 3 hours. ~ pure type-~ zeolite having the following particle spectrum is obtained:
fraction proportion (% by weight) < 3 ~m 21%
< 5 ~m 76%
<10 llm 97%
<15 llm 98%
The proportion of 50% by weight is below 3.8 ~m. ~, The particle size is determined by measuring with the Coulter counter.
- Examp e 2 Perborate-Containing Detergent 45.0% by weight of sodium aluminium silicate obtained according to example 1 (dried for 6 hours at 90C, water content 16.8% by weight), 20.0% by weight of sodium perborate, 35.0% of a detergent powder, produced,for example, by -hot-air drying and having the following composition:
21.0% by weight of ABS (dodecyl benzene sulphonate), 7.5% by weight of ethoxylated tallow alcohol (1 mole of tallow alcohol + 14 moles of ethylene oxide), 7.2% by weight of soap (sodium salt of saturated substantiallY C18-C22 fatty acids), 9% by weight of sodium tetrasilicate (Na2O
3.3 SiO2),
4.5% by weight of magnesium sulphate, 2.0% by weight of carboxy-methyl cellulose, 0.6% by weight of optical brightener 9.0% by weight of soluble complexing-agent salt lOl~Z162 (for example, sodium citrate, NTA, EDT~, sodium triphosphate and l'OC), 35.0% by weight of sodium sulphate the rest = water.
The detergent was produced by mixing the three powdered components.
Example 3 Detergent Free from Perborate 2.0% by weight of ethoxylated Cll/C15 oxo alcohol (1 mole of oxo alcohol + 3 moles of ethylene oxide),
The detergent was produced by mixing the three powdered components.
Example 3 Detergent Free from Perborate 2.0% by weight of ethoxylated Cll/C15 oxo alcohol (1 mole of oxo alcohol + 3 moles of ethylene oxide),
5.0~ by weight of ethoxylated Cll/C15 oxo alcohol (1 mole of oxo alcohol + 3 moles of ethylene oxide), 40.0% by weight of sodium aluminium silicate obtained according to example 1 (dried for 6 hours at 90C, water content 16.8% by weight), 15.0~ by weight of soda, -5.0% by weight of sodium citrate, 4.0% by weight of sodium tetrasilicate (Na2O 3.3 SiO2), 1.5% by weight of carboxy-methyl cellulose, 0.2% by weight of optical brightener, 23.0% by weight of sodium sulphate, rest = water +) replaceable by tallow alcohol + 5 moles of ethylene oxide, ++) replaceable by tallow alcohol + 14 moles of ethylene oxide.
The detergent is produced by spraying ethoxylation products (non-ionic tensides) on the powder particles consisting of the other components.
'
The detergent is produced by spraying ethoxylation products (non-ionic tensides) on the powder particles consisting of the other components.
'
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A crystalline type-A zeolite powder having the composition 1.0 ? 0.2 M2/nO: Al2O3 : 1.85 ? 0.5 SiO2 ? y H2O, wherein M represents a metal cation, n its valency and y a value of up to 6, and containing 50% by weight of particles of a size below a maximum of 4.3 µm as well as having the following particle spectrum fraction proportion (µm) (% by weight) < 3 18 to 38 < 5 70 to 82 <10 93 to 99 <15 96 to 100
2. A process for producing the zeolite powder of claim 1 by hydrothermal crystallization of an alkali metal aluminate/
water/silicate synthesis mixture containing SiO2, Al2O3, Na2O
and water, in which an alkali silicate solution is added over a period of 10 to 200 minutes, while stirring or subjecting to the action of shearing forces to an aqueous sodium aluminate liquor having a temperature of 30 to 100°C and containing 0.1 to 100 g of Al2O3 per litre and 1 to 200 g of Na2O per litre so that a clear reaction mixture having the composition SiO2/Al2O3 = 50 to 1000, Na2O/SiO2 = 0.2 to 20 and H2O/Na2O = 4 to 300 is obtained, whereupon, over a period of 5 to 200 minutes, a sodium aluminate liquor having a temperature of 30 to 100°C and containing 10 to 250 g of Na2O per litre and 10 to 200 g of Al2O3 per litre is added while stirring or subjecting to the action of the shearing forces and that the synthesis mixture thus obtained is allowed to crystallize at a temperature between 20 and 175°C within at least 15 minutes.
water/silicate synthesis mixture containing SiO2, Al2O3, Na2O
and water, in which an alkali silicate solution is added over a period of 10 to 200 minutes, while stirring or subjecting to the action of shearing forces to an aqueous sodium aluminate liquor having a temperature of 30 to 100°C and containing 0.1 to 100 g of Al2O3 per litre and 1 to 200 g of Na2O per litre so that a clear reaction mixture having the composition SiO2/Al2O3 = 50 to 1000, Na2O/SiO2 = 0.2 to 20 and H2O/Na2O = 4 to 300 is obtained, whereupon, over a period of 5 to 200 minutes, a sodium aluminate liquor having a temperature of 30 to 100°C and containing 10 to 250 g of Na2O per litre and 10 to 200 g of Al2O3 per litre is added while stirring or subjecting to the action of the shearing forces and that the synthesis mixture thus obtained is allowed to crystallize at a temperature between 20 and 175°C within at least 15 minutes.
3. A process as claimed in claim 2, in which the sodium aluminate liquor having a content of 250 g/l Na2O and 10 to 200 g/l Al2O3 is added in two stages, the rate of addition in the second stage being 2 to 10 times greater than the first stage.
4. A process as claimed in claim 2, in which the subsequent tempering is effected.
5. A process as claimed in claim 4, in which the tempering is effected at a temperature between 85°C and 105°C
in the crystallization mother liquor.
in the crystallization mother liquor.
6. A process as claimed in claim 5, in which the tempering time is from 0.2 to 6 hours.
7. A process as claimed in claim 6, in which the tempering time is from 0.8 to 4 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762651436 DE2651436A1 (en) | 1976-11-11 | 1976-11-11 | TYPE A III CRYSTALLINE ZEOLITE POWDER |
| DEP2651436.3-41 | 1976-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1082162A true CA1082162A (en) | 1980-07-22 |
Family
ID=5992893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA289,971A Expired CA1082162A (en) | 1976-11-11 | 1977-11-01 | Crystalline type-a zeolite powder iii |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4305916A (en) |
| JP (3) | JPS5360899A (en) |
| BE (1) | BE860756A (en) |
| BR (1) | BR7707379A (en) |
| CA (1) | CA1082162A (en) |
| CH (1) | CH631946A5 (en) |
| DE (1) | DE2651436A1 (en) |
| ES (1) | ES463995A1 (en) |
| FR (1) | FR2370692A1 (en) |
| GB (1) | GB1571539A (en) |
| IT (1) | IT1143828B (en) |
| NL (1) | NL177201C (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2651419A1 (en) * | 1976-11-11 | 1978-05-18 | Degussa | TYPE A IV CRYSTALLINE ZEOLITE POWDER |
| DE3007080A1 (en) * | 1980-02-26 | 1981-09-10 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING TYPE A CRYSTALLINE ZEOLITE POWDER |
| DE3007087A1 (en) * | 1980-02-26 | 1981-09-10 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING ZEOLITE A |
| DE3007044A1 (en) * | 1980-02-26 | 1981-09-10 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING CRYSTALLINE ZEOLITE A |
| DE3007123A1 (en) * | 1980-02-26 | 1981-09-10 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING ZEOLITE A |
| DE3132379A1 (en) * | 1981-08-17 | 1983-02-24 | Degussa Ag, 6000 Frankfurt | ZEOLITE GRANULES, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3132928C1 (en) | 1981-08-20 | 1983-01-13 | Degussa Ag, 6000 Frankfurt | Process for accelerating the setting of hydraulic cement mixtures |
| DE3208598A1 (en) * | 1982-03-10 | 1983-09-22 | Degussa Ag, 6000 Frankfurt | METHOD FOR THE PRODUCTION OF ZEOLITES MODIFIED WITH ORGANOSILANES |
| IN157422B (en) * | 1982-06-21 | 1986-03-22 | Lever Hindustan Ltd | |
| JPS6122184A (en) * | 1984-07-10 | 1986-01-30 | 株式会社山本製作所 | Method of controlling burner for generating hot air in cereal grain drier |
| DE3444311A1 (en) * | 1984-12-05 | 1986-06-05 | Degussa Ag, 6000 Frankfurt | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS |
| DE3516660A1 (en) | 1985-05-09 | 1986-11-13 | Degussa Ag, 6000 Frankfurt | POWDER-BASED BINDER CONCENTRATE |
| JPS62212528A (en) * | 1986-03-14 | 1987-09-18 | Tanita:Kk | Electronic balance |
| JPS63135825A (en) * | 1986-11-28 | 1988-06-08 | Ishida Scales Mfg Co Ltd | Apparatus for automatically alarming time for adjustment of machine |
| US5474753A (en) * | 1990-11-09 | 1995-12-12 | Laviosa Rhone-Poulenc | Preparation of crystalline 4A zeolites |
| JP2602384B2 (en) * | 1991-12-27 | 1997-04-23 | 新日本製鐵株式会社 | Atmosphere control method and apparatus for heat treatment furnace |
| DE4309656A1 (en) * | 1993-03-25 | 1994-09-29 | Henkel Kgaa | Process for the production of very finely divided zeolitic alkali metal aluminum silicates |
| US7052541B2 (en) * | 2002-06-19 | 2006-05-30 | Board Of Regents, The University Of Texas System | Color compositions |
| US7425235B2 (en) * | 2005-02-11 | 2008-09-16 | The Board Of Regents Of The University Of Texas System | Color compositions and methods of manufacture |
| EP1902101A2 (en) * | 2005-06-17 | 2008-03-26 | The Board of Regents of The University of Texas System | Organic/inorganic lewis acid composite materials |
| JP4903513B2 (en) * | 2006-07-19 | 2012-03-28 | サンデン株式会社 | Beverage mixing device and vending machine using the same |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1038017B (en) | 1953-12-24 | 1958-09-04 | Union Carbide Corp | Process for making crystalline zeolitic molecular sieves |
| US2882243A (en) * | 1953-12-24 | 1959-04-14 | Union Carbide Corp | Molecular sieve adsorbents |
| US3058805A (en) * | 1958-10-03 | 1962-10-16 | Bayer Ag | Process for the production of sodium zeolite a |
| US3310373A (en) | 1963-04-03 | 1967-03-21 | Mobil Oil Corp | Method for producing crystalline aluminosilicates |
| SE419975C (en) * | 1973-04-13 | 1986-08-18 | Henkel Kgaa | DETERGENTS AND / OR BLENDS CONTAINING A CRYSTALLINE WATER-INSULATED SILICATE PROCEDURE FOR ITS PREPARATION AND USE |
| AT330930B (en) | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES |
| US4605509A (en) * | 1973-05-11 | 1986-08-12 | The Procter & Gamble Company | Detergent compositions containing sodium aluminosilicate builders |
| CA1037815A (en) * | 1973-06-20 | 1978-09-05 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Process for the production of solid, pourable washing or cleaning agents with a content of a calcium binding silicate |
| DE2433485A1 (en) * | 1973-07-16 | 1975-02-06 | Procter & Gamble | ALUMINOSILICATE ION EXCHANGERS SUITABLE FOR USE IN DETERGENTS |
| US3985669A (en) * | 1974-06-17 | 1976-10-12 | The Procter & Gamble Company | Detergent compositions |
| DE2447021C3 (en) | 1974-10-02 | 1984-03-22 | Degussa Ag, 6000 Frankfurt | Type A crystalline zeolite powder and the process for its preparation |
| DE2517218B2 (en) | 1975-04-18 | 1977-05-05 | Henkel & Cie GmbH, 4000 Düsseldorf; Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, 6000 Frankfurt | TYPE A CRYSTALLINE ZEOLITE POWDER |
| US4041135A (en) * | 1975-07-25 | 1977-08-09 | J. M. Huber Corporation | Production of high capacity inorganic crystalline base exchange materials |
-
1976
- 1976-11-11 DE DE19762651436 patent/DE2651436A1/en not_active Ceased
-
1977
- 1977-08-22 NL NLAANVRAGE7709247,A patent/NL177201C/en not_active IP Right Cessation
- 1977-09-21 FR FR7728475A patent/FR2370692A1/en active Granted
- 1977-09-29 IT IT69148/77A patent/IT1143828B/en active
- 1977-10-27 US US05/846,017 patent/US4305916A/en not_active Expired - Lifetime
- 1977-11-01 CA CA289,971A patent/CA1082162A/en not_active Expired
- 1977-11-03 BR BR7707379A patent/BR7707379A/en unknown
- 1977-11-10 CH CH1374577A patent/CH631946A5/en not_active IP Right Cessation
- 1977-11-10 JP JP13520177A patent/JPS5360899A/en active Pending
- 1977-11-10 BE BE6046218A patent/BE860756A/en not_active IP Right Cessation
- 1977-11-10 ES ES463995A patent/ES463995A1/en not_active Expired
- 1977-11-11 GB GB47036/77A patent/GB1571539A/en not_active Expired
-
1981
- 1981-04-08 JP JP56051919A patent/JPS5761619A/en active Granted
- 1981-04-08 JP JP56051920A patent/JPS5761097A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NL7709247A (en) | 1978-05-16 |
| BR7707379A (en) | 1978-08-01 |
| IT1143828B (en) | 1986-10-22 |
| ES463995A1 (en) | 1978-07-16 |
| BE860756A (en) | 1978-05-10 |
| JPS5761619A (en) | 1982-04-14 |
| GB1571539A (en) | 1980-07-16 |
| JPS6324927B2 (en) | 1988-05-23 |
| NL177201B (en) | 1985-03-18 |
| NL177201C (en) | 1985-08-16 |
| DE2651436A1 (en) | 1978-05-18 |
| US4305916A (en) | 1981-12-15 |
| JPS5360899A (en) | 1978-05-31 |
| FR2370692B1 (en) | 1980-04-11 |
| CH631946A5 (en) | 1982-09-15 |
| FR2370692A1 (en) | 1978-06-09 |
| JPS5761097A (en) | 1982-04-13 |
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